Composition of terpinene-maleic anhydride hydrogenated coumaroneindene resin, and polystyrene



Patented Feb. 17, 1948 COMPOSITION OF TERPINENE-MALEIC AN- HYDRIDE.HYDROGENATED COUMARONE- INDENE RESIN, AND POLYSTYRENE Irving 0. Matthewsand William F. Lynch, Rochester, N. Y., assignors to Eastman KodakCompany, Rochester, N. Y., a corporation of New Jersey No Drawing.

1940, Serial No.

Original application January 24, 815,400, now Patent No.

2,328.566, dated September 7, 1943. Divided and this application January7, 1943, Serial No. 471,584. In Canada August 15, 1938 1 Claim.

This is a'division or our pending application Serial No. 315,400, filedJanuary 24, 1940, now Patent No. 2,328,566 issued Sept. 7, 1943, for aComposition of matter and the present invention relates to homogeneousmixtures containing two or three synthetic resins. Said composition ofmatter, according to the invention, may be dissolved in solvents to forman all-purpose protective coating or may be used as a plastic for theproduction of molded articles.

Synthetic resins have been used individually as protective coatings andplastics, but when so used have been lacking in heat resistance, havehad low chemical and atmospheric corrosion resistance, have been brittleand/or are subject to checking. When used as or in protective coatings,said individual synthetic resins have poor adhesion and are difilcult toapply, such as being subject to cobwebbing during spraying.

The primary object of the present invention is the provision of acomposition of matter which is remarkably tough and corrosion-resistant,and which produces a protective film or coating of exceptional adhesionand freedom from checking. Other objects of the invention will beapparent to those skilled in the art from the following disclosure.

Our improved composition of matter comprises a mixture or combination oftwo or more of the following resins: a reaction product of a polybasicor alpha-beta-dicarboxylic acid anhydride and terpinene: a hydrocarbonor cyclo-olefin resin: and a styrol resin.

2 reaction product in the still. The preferred reaction product istechnically known'as 3-lsopropyl 6 methyl 3,6 indoethylene-A -tetrahydrophthalic anhydride.

In order further to enhance particular qualities, such as the gloss,flexibility or adhesion, of the final composition or matter, saidreaction product of a polybasic acid anhydride and terpinene may, ifdesired, be modified in anyone of several known ways. For instance, saidreaction product may be modified by blending with a dry- The reactionproduct or a polybasic or of an alpha-betwdicarboxylic acid anhydrideand terpinene to be employed in the composition according to theinvention may be prepared as follows.

Alpha-terpinene may be obtained by the fractionation of pine oil usingthe fraction boiling within about the range of (178-182) C., and about480 grams of such alpha-terpinene may be heated with about 294 grams ofmaleic anhydride, or alternatively with an equivalent quantity of maleicacid, at a temperature to cause gentle boiling, say about 150-200 C. fora period of about five hours. If necessary or desirable, said reac-'tion product may be further purified or refined by distillation under adiminished pressure by which procedure terpinene and impurities will berendered volatile and so removed from the final log oil, with anothersynthetic resin, or with a natural resin such as rosin. Such methods ofmodification may or may not involve the use of heat, or may include theuse of a common solvent and the modifying agent may be introduced beforeor after the reaction is completed, or may constitute the solvent inwhich the reaction occurs. Preferably and especially for compounding. anall-purpose protective coating. said reactionproduct oi a polybasic acidanhydride and terpinene is modified by heating said reaction producttogether with natural rosin.

The hydrocarbon or cyclo-olefin resins to be used are preferablyoi thecoumarone-indene type and may be obtained by the catalyticpoiymerization ol'resin-iorming bodies contained in crude solventnaphtha, and other hydrocarbon liquids, containing bodies polymerizableto form resins oi the coumarone-indene type.

Specifically, two commercial forms ofhydrocarbon resins have been usedsatisfactorily in the composition of the invention. One a synthetichydrocarbon resin essentially consisting oi dicyclopentadiene polymerand a few per cent of coumarone-indene polymer. The other a syn thetichydrocarbon resin including coumaroneindene with other polymerizablehydrocarbons which is recognized as a, hydrogenated couma rone-indenehydrocarbon resin resulting from the catalytic polymerization. andhydrogenation oi the resin-forming bodies contained in crude aromaticnaphtha, as described in U. 8. Patent No, 2,319,959 of Tierney (seeparticularly page 2, golumn 2, lines 1-27 page 1, column 2, lines 35-The styroi resin may be made by polymerization of styrene to polystyreneand which polymerization may be accomplished by any of the well knownmethods or by simply heating the 3 liquid styrene to a temperatureapproximately between 200' and 800 C. and holding the material at thattemperature until complete polymerization takes'piace.

A composition of matter having exceptional hardness, good flexibility,and chemical and weather corrosion resistance comprises a physicalmixture or -30 parts of the reaction product of a polybasic acidanhydride and terpinene, -40 parts of a hydrocarbon resin, and 70-50parts of a polystyrol resin. By eliminating the hydrocarbon resin andcompounding 20-80 parts oi a reaction product of a polybasic anhydrideand terpinene with 80-20 parts of polystyrene, a composition of matteris obtained which has good hardness and adhesion and which hasparticularly good weather resistance.

The hydrocarbon resin may be either the coumarone-indene resin or may bethe hydrocarbon resin composed primarily of dlcyolopentadiene but thedicyclopentadiene resin is preferred because of better adhesion andparticularly for compositions which are to be subjected to'ultravioletlight.

Example The composition of matter according to the invention andcomprising a reaction product of alphata-dicarboxylic acid anhydride andalpha-te inene, a hydrocarbon resin, and a styrol resin is preferablyprepared by physically mixing 20 parts or the reaction product of maleicacid anhydride and alpha-terpinene, parts or cyclooleiln resin and 60parts of polystyrene. To form a lacquer, the mixture is dissolved in asuitable quantity of a solvent, such a solvent may comprise 50% toluene,25% xylene, 12%% amyl acetate'. and 12%% coal tar solvent naphtha. Filmsformed of such lacquer are exceptionally hard, and have great resistanceto corrosion. However.

such corrosion resistance is markedly increased when the cycle-olefinresin is in the form of dicyclopentadiene, Films formed from thismodified mixture have been found to resist the action of strongoxidizing reagent, notably silver nitrate solution.

understood that the ingredients and proportions of the mixture may bevaried considerably within the ranges given, and for instance if slowdrying films or slow drying adhesives are required the solvent mixturemay be modified by the addition or substitution of comparatively highboiling solvents which are compatible with the other ingredients used.On the other hand, as is known, quick drying films or adhesives areobtained by the addition or substitution of comparatively low boilingsolvents to the solvent mixture.

Having now particularly described our invention, what we desire tosecure by Letters Patent of the United States and we claim is:

As a composition of matter a homogeneous mass essentially consisting of10-30 parts of a reaction product or terpinene and maleic anhydride,20-40 parts of a. hydrogenated coumaroneindene hydrocarbon resinresulting from the catalytic polymerization and hydrogenation of theresin-forming bodies contained in crude aromatic naphtha. and -50 partsof a polystyrene resin.

IRVING C. MATTHEWS. WILLIAM F. LYNCH.

REFERENCES CITED The following references are of record in the tile ofthis patent:

UNITED STATES PATENTS Number Name Date 2,174,885 Kaliander Oct. 8, 19392,294,651 Billing Sept. 1. 1942 2,319,959 Tierney May 25, 1943 OTHERREFERENCES

